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CONTENTS
MOLECULAR WEIGHTS OF POLYMERS
INTRINSIC VISCOSITY
GEL PERMEATION CHROMATOGRAPHY
MASS SPECTROMETRY
INSTRUMENTATION FOR MOLECULAR
WEIGHT DETERMINATION
SOLUTION THERMODYNAMICS AND
MOLECULAR WEIGHTS
3.7
3.8
3.9
3.10
3.11
3.12
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3.7 MOLECULAR WEIGHTS OF POLYMERS

3.7.1 Molecular Weight of Commercial
Polymers
Commercial use30,000-1,000,000 g/mol


High enough
molecular weights to
obtain good physical
properties
Low enough molecular
weights to permit
reasonable processing
conditions
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3.7.2 Thermodynamics and
Kinetics of Polymerization
Thermodyna
mics
Kinetics
The molecular
weights and
the
polydispersity
index
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AFFECT
3.7.2.1 Thermodynamics of Chain
Polymerization
K RT G ln
0
=
Consider a chain polymerization of monomer M:
- + -
+1 n n
M M M
The rate constant of the forward reaction, polymerization, is k
p

The rate constant of the reverse reaction, depolymerization, is given by k
dp
] [
1
] ][ [
] [
1
M M M
M
k
k
K
n
n
dp
p
=
-
-
= =
+
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Ceiling temperaturestemperatures above which the
monomer cannot be polymerized,but the polymer will
spontaneously depolymerize back to the monomer.

Commercially this fact leads to an important method
of polymer recycling whereby scrapped polymer is
heated under anaerobic conditions to allow distilling
off the resultant monomers.
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) ( ) (
m p m p
S S T H H S T H G = =
3.7.2.2 Kinetics of Chain Polymerization
- + -
-
RM M R
R I
k
k
i
2
2
Initiation
Propagation:
- + -
. .
- + -
+1 n n
2
RM M RM
RM M RM
p
p
k
k
Termination by
combination
R RM RM RM
k
m n m n
tc
+
- + -
Termination by
disproportionation
m n m n
td
RM RM RM RM
k
+ - + -
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R
p
represents the rate of polymerization
2 / 1
2 / 1
] ][ [ I M
k
k
k R
t
i
p p
|
|
.
|

\
|
=
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Kinetic chain length:
Radical chain polymerization is the average
number of monomer molecules consumed for
each radical initiating a chain.Thus, at steady
state:

2 / 1
]) [ ( 2
] [
I k fk
M k
R
R
R
R
v
t i
p
t
p
i
p
= = =
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3.7.2.3 Thermodynamics of Step Polymerization
Polyesterification where carboxyl groups and
hydroxyl groups react to form a polyester and water;



The equilibrium constant, K:

O H COO OH COOH
K
2
+ +
] ][ [
] ][ [
2
OH COOH
O H COO
K =
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p:fractional conversion

number-average degree
of polymerization



weight-average degree
of polymerization



Polydipersity Index

p
DP
n

=
1
1
p
p
DP
w

+
=
1
1
p
DP
DP
PDI
n
w
+ = = 1
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3.7.2.4 Kinetics of Step
Polymerizations
Step
polymerizations

Self-
catalyzed
External-
catalyzed
Catalyzed by
some externally
added chemical
such as an acid
Step
Polymerizations
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Self-catalyzed polymerization


] [ ] [
] [
2
OH COOH k
dt
COOH d
=

O H COO OH COOH
COOH
2
+ +

]) [ ] [ (
3
OH COOH c kc
dt
dc
= = =

p
DP p c c
n

= =
1
1
), 1 (
0
1 2
) 1 (
1
2
0
2
2
+ =

= kt c
p
DP
n
} }
=

t c
c
kdt
c
dc
0
3
0
kt
c
c
2
1 1
2 2
0
=
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3.7.3 Molecular Weight Distributions
Chain polymerization
Termination by disproportionation:PDI=2
Termination by combination:PDI=1.5
Stepwise polymerizations, such as polyester
formation,PDI=1+p=2
Anionic polymerizations :narrow distribution, sometimes
PDI<1.05.
Polymers in nature
Proteins:almost the only source of truly monodisperse
polymers, PDI=1
Cellulose have very broad distributions.

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The various molecular weight distributions have been
modeled. Two of the most important are the Schultz
distribution and the Poisson distribution.
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3.7.4 Gelation and Network
Formation
Linear:
functionality of the
monomer is 2
Branched or cross-linked:
trifunctional, tetrafunctional,
or higher

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3.7.4 Gelation and Network
Formation
gelation point:


2 / 1
) 1 (
1

=
f
P
c
f :the functionality of the branch
units
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3.8 INTRINSIC VISCOSITY
Both the colligative and the scattering methods result
in absolute molecular weights; that is, the molecular
weight can be calculated directly from first principles
based on theory.
Defects : Slow Expensive;
In order to handle large numbers of samples,
especially on a routine basis, rapid, inexpensive
methods are required. This need is fulfilled by
intrinsic viscosity and by gel permeation
chromatography.
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Flow rate & Shear rate
Frictional drag and
rotational forces
Viscosity increase by
the polymer in the
solution.

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Mechanism of viscosity
increase:
3.8.1 Definition of Terms
Solvent viscosity:
Polymer solution viscosity:

Relative viscosity:

Specific viscosity:
0

0
rel

=
1

rel
0
0
sp
= =
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Intrinsic viscosity:
0
] [

=
c
sp
c

] [
ln
2
ln
2
) 1 ln( ln
0
2
2
2

=
(

|
|
.
|

\
|
~
+ = + =
c
rel
sp sp
rel
sp
sp sp rel
c
c
c
c c
For dilute solutions:

Inherent viscosity:

c
rel
ln
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Two sets of units are in use for [].
The American units are 100 cm
3
/g,
The European units are cm
3
/g.
Of course, this results in a factor of 100 difference in
the numerical result. Lately, the European units are
becoming preferred.
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3.8.2 The Equivalent Sphere
Model
In assuming a dilute dispersion of uniform, rigid,
noninteracting spheres,
Einstein derived an
equation expressing
the increase in viscosity
of the dispersion


the quantity v
2
represents
the volume fraction of spheres

2 0
v 5 . 2 1+ =
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In shear flow, it exhibits a frictional
coefficient of f
0
. Then according to Stokes
law

Re:a hydrodynamic sphere of equivalent radius

The Einstein viscosity relationship for
spheres may be written:


e
R f
0 1 0
6 =
e sp
V
V
n
|
.
|

\
|
= =

2 0
5 . 2

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M
cN
V
n
A
=
2

| |
|
|
.
|

\
|
=

= =
(

1 3
1
3 1
e
0
5 . 2 g cm
mol g
cm mol
M
V N
c
A
c
sp

2 / 1
2 / 3
2
e 1
3
e 1 e
3
4
3
4
M
M
R
M
R
M
V
|
|
.
|

\
|
= =

Note
that:
| |
3 2 / 1
2 / 3
0
A
1
3
4
5 . 2 o M
M
R
N
e
|
.
|

\
|
=

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is the expansion of the coil in a good
solvent over that of a Flory -solvent
o
0 e e
R R =
3.8.3 The MarkHouwink
Sakurada Relationship
In the late 1930s and 1940s Mark, Houwink, and
Sakurada arrived at an empirical relationship between
the molecular weight and the intrinsic viscosity:
a
v
KM = ] [
K and a are constants for a particular polymer
solvent pair at a particular temperature.
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More generally, it should be pointed out that a varies from
0 to 2; see Table 3.11.
0.5
( Flory -solvent )
0.8
(thermodynamicall
y good solvent)
a
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3.8.4 Intrinsic Viscosity
Experiments
In most experiments, dilute solutions of about 1%
polymer are made up.
The quantity
rel
should be about 1.6 for the highest
concentration used.
The most frequently used instrument is the
Ubbelhode viscometer, which equalizes the pressure
above and below the capillary.
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Huggins equation


Kraemer equation


Algebraically:

If either of these requirements is not met, molecular
aggregation, ionic effects,or other problems may be
indicated.

c k
c
sp
2
] [ ' ] [

+ =
c k
c
rel
2
] [ ' ' ] [
ln

=
5 . 0 ' ' ' = +k k
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While use of the viscosity-average molecular weight of
a polymer in calibrating K and a in equation,MV
values usually are not initially known.
The calibration problem may be alleviated by one or
more of the following methods:
1. Use of fractionated polymers.
2. Use of polymers prepared with narrow molecular
weight distributions,such as via anionic polymerization.
3. Use of weight-average molecular weight of the
polymer, since it is closer than the number-average
molecular weight.
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3.8.5 Example Calculation
Involving Intrinsic Viscosity
We dissolve 0.10 g of the polymer in 100 ml of
butanone and measure the flow times at 25in an
Ubbelhode capillary viscometer. The results are
sample time
Pure butanone

110 s

0.10% Polystyrene solution

140 s

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3.9 GEL PERMEATION
CHROMATOGRAPHY
Gel permeation chromatography (GPC), sometimes
called size exclusion chromatography (SEC), makes
use of the size exclusion principle.
The size of the molecule, defined by its hydrodynamic
radius, can or cannot enter small pores in a bed of
cross-linked polymer particles, the most common
form of the stationary phase.
The smaller molecules diffuse in and out of the pores
via Brownian motion (see Figure 3.16) and are delayed.
The larger molecules pass by and continue in the
mobile phase.
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The stationary phase consists of small, porous particles.While the mobile
phase flows at a specified rate controlled by the solvent delivery system, the
sample is injected into the mobile phase and enters the columns.
The length of time that a particular fraction remains in the columns is called
the retention time .
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As the mobile phase
passes the porous
particles, the
separation between
the smaller and the
larger molecules
becomes greater
(see Figure 3.18) .
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3.9.1 Theory of Gel Permeation
Chromatography
molecular
weight
distribution
(MWD)
Mw/Mn
chemical
composition
Statistical
Alternating
Block
Graft
functionality
End groups
shape of
the chain
Random coils
Rod shaped
Rings
Most polymers
exhibit some
form(s) of
heterogeneity
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3.9.2 Utilization of Distribution
Coefficients in GPC and HPLC
phase stationary the of volume
column the of volume ial interestit solute the of volume retention
=
d
K
V
V V
K
i R
d

=
phase mobile in the ion concentrat analyte
phase stationary the to attached or in ion concentrat analyte
=
d
K
Kd : the distribution coefficient
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the quantity K
d
is related to the Gibbs free energy, G,


After rearranging, we have



S: The limited dimensions of the pores relative to the size
of the polymer chains causes S of the polymer chains to
decrease.
Interactions between the pore walls and the polymer
chains are expressed in changes in H, and are negative if
the polymer and the wall are attracted to each other.

G S T H K RT
d
A = A A = ln
|
.
|

\
|
A

A
=
RT
H
R
S
K
d
exp
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In the general case, Kd may be expressed


the subscripts GPC and HPLC indicate quantities
involving only entropic or enthalpic interactions,
respectively.
In the ideal GPC case, K
HPLC
equals unity, and Kd =
KGPC.


HPLC GPC d
K K K =
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3.9.3 Types of Chromatography
GPC, which uses porous particles to
separate molecules of different sizes.

HPLC, by contrast, utilizes interactions
between the polymers and the surface
of the particles composing the
stationary phase.
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Instruments today are sometimes called universal
HPLCs, containing both GPC and HPLC columns and
measurement capability; see Table 3.12 for
specifications.

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3.9.4 GPC Instrumentation
The most important parts of the instruments are :
the column
types for the
molecular
weight range
of analysis
the detector
system
the pumps for
maintaining
constant,
pulseless rates
of flow
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3.9.5 Calibration
Noting GPC is a relative molecular weight method,
such instrumentation needs to be calibrated. Narrow
molecular weight distribution, anionically synthesized
polystyrenes are used most often for the purpose.
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Figure 3.20 The molecular weight and molecular weight
distribution are determined with standards precalibrated
via an absolute method such as light-scattering.
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3.9.6 Selected Current Research
Problems
In the case of copolymers, any single detection method
will have variable sensitivity for each type of mer.
If the copolymer composition is itself a variable, then
the use of dual or even multiple detectors will be
required for accurate results.
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The molecular weight of each component in a polymer
blend may also be determined.
In a model experiment, poly(methyl methacrylate),
PMMA, molecular weights were estimated in the
presence of polystyrene, PS.
Anionically polymerized polystyrene and free radically
polymerized poly(methyl methacrylate) were
dissolved in tetrahydrofuran in a 50/50 w/w mix.
A dual detector GPC was used, equipped with
refractive index (RI) and ultraviolet (UV) detectors.
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Figure 3.22 Analysis of the molecular weights of the polymers in a
polymer blend of polystyrene and poly(methyl methacrylate).
This method requires a dual detector GPC system.
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Current research problems include chain geometry
and solution aggregation , ABC triblock copolymers as
topological isomers , and hyperbranched polymers
(85); see Section 14.5.
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3.9.7 The Universal Calibration
( )
3
2 / 3
2
0
] [ o r M u =
Figure 3.23 The universal calibration curves for polystyrene and poly(vinyl
acetate) (94). The number 5 in the x-axis units means that the scale is in
siphon counts of 5 cm3, so that the x-ordinate 30 corresponds to an
elution volume of 150 cm3. (R. Dietz, private communication,November
1984.) Mr is the peak GPC molecular weight, usually the unknown, Mr
values are close to the geometric mean of Mn and Mw.
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The right-hand side is proportional to the polymers
hydrodynamic volume.
This is the universal calibration, which calls for a plot
of []M versus elution volume.
It cannot be used for highly branchedmaterials or
polyelectrolytes, which have different or varying
hydrodynamic volume relationships.

( )
3
2 / 3
2
0
] [ o r M u =
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3.9.8 Properties of Cyclic Polymers
The properties of the linear and cyclic polymers are
compared in Figure 3.24 .
1. The more compact cyclic polymers possessed smaller
hydrodynamic volumes (i.e., they eluted later via GPC
in Figure3.24A).
2. They had lower intrinsic viscosities than their linear
analogs, with []cyclic/[]linear = 0.4 (Figure 3.24B).
3. The root-mean-square radius of gyration, Rg, was
measured using GPC coupled to a multiangle light-
scattering detector. Figure 3.24C.
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3.10 MASS SPECTROMETRY
Mass spectrometry is the study of the mass, or
molecular weight, of ions created via ionization or
fragmentation and determined electrically in the gas
phase.
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In the study of polymers, mass spectrometry has two
broad applications:
1. To characterize functionality. Unknown
polymers, residual volatile chemicals, and
additives can be identified.
2. To provide a new basis for the determination
of absolute molecular weights.
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3.10.1 High Molecular Weight
Studies
The spectrum shows three different charge states
centered at about m/z of 17,000, 32,000, and 65,000
g/mol.
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3.10.2 Advances Using MALDI
Techniques
Matrix-assisted laser desorption ionization (MALDI)
Typical MALDI matrices are aromatic organic acids. A
small aliquot of the mixture is applied to the MALDI
target and solidifies as the solvent evaporates.
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3.10.2.1 Small Sample Size
Very tiny amounts of polymer are utilized.
For example, an analyte solution contains 5 mg/ml.
Approximately 0.30.5 mLof this solution are placed on
the target.
With these very small samples,an electrospray
technique was found to give more reproducible results
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3.10.2.2 Oligomer and Telomer-
Type Studies
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3.10.2.3 Calibration of Results
The molecular weights reported by the laboratories gave
values slightly lower than the measurements made by
the classical methods.
However, there was evidence that the MALDI method
was probably the more accurate.
For example, traces of dust raise the apparent molecular
weight obtained via lightscattering.
Overall, however, good agreement was obtained.
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3.11 INSTRUMENTATION FOR MOLECULAR
WEIGHT DETERMINATION
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3.12 SOLUTION THERMODYNAMICS
AND MOLECULAR WEIGHTS
Below the Flory -temperature, polymer solutions may
phase-separate.The higher the molecular weight is, the
higher the upper critical solution temperature.
At infinite molecular weight, the Flory -temperature
is reached. Thus the Flory -temperature is defined by
several different criteria:

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1. It is the temperature where A2 is zero for dilute
solutions, and 1 = 1/2.
2. It is the temperature where the radius of gyration
approximates that of the bulk polymer (see Chapter 5).
3. It is the temperature at which an infinite molecular
weight fraction would just precipitate (see Chapter 4).
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The methods are divided into absolute methods, which
determine the molecular weight from first principles,and
relative methods, which depend on prior calibration.The latter
are usually selected because they are fast and inexpensive.
Values obtained from the several methods are summarized in
Table 3.15.
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